PSG has now claimed the season-opening trophy on fourteen separate times.
The Parisian giants required a dramatic equaliser followed by a perfect spot-kick decider to get past their arch-rivals in the Gulf and secure a fourth straight French Super Cup victory.
The Champions League holders appeared to be coasting towards a straightforward triumph in the showdown between the French league champions and the French Cup winners after Ousmane Dembele found the net early on.
Yet, the southern French side struck twice late to seize a shock lead. Initially, Mason Greenwood converted from the spot-kick, before the defender inadvertently turned the ball into his own net for an own-goal.
In a breathtaking turn of fortune, Goncalo Ramos grabbed a crucial equaliser in the dying seconds to send the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, saving decisive kicks from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored with composure for PSG to seal a 4-1 shootout victory.
Now 14-time champions PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now won this trophy for the 12th time in the past 13 seasons.
